Human milk oligosaccharides (HMOS) is the third abundant solid component after lactose and fat in human milk with diverse benefits. The key issue of HMOS research is the sensitive and quantitative analysis methods. Since HMOS are complex mixture with various structures and isomer, and are without inner chromophores, HMOS are difficult to identify and quantify. This review is to summarize the new and emerging methods for oligosaccharide analysis.